Divergent synthesis of looped poly(ester)-and poly(ether)-substituted dendrons and dendrimers

Abstract

The present invention describes a process for preparing new looped dendrimer and dendron compounds by controlling the molar amount of branch cell reagent monomer that is combined with various cores bearing core-XR functionalities (e.g., primary, or secondary amines, thiol, or epoxy functionalities). These looped, macrocyclic structures are more robust to various conditions, with greater resistance to acid/base hydrolysis. Alternatively, the looped, macrocyclic structure may offer new orientations that would qualify it as a better chelation ligand for metals, and other similar uses.

1 . Dendrimers and dendrons comprising a looped, macrocyclic structure in one or more branches of the formula 
       
         
           
           
               
               
           
         
         wherein:
 [C] is the core of the dendrimer or dendron that may have more than 1 branch arm depending on the number of core-XR functionalities present; 
 XR represents the core functionalities and when R═H is a mono-alkyl amine, an α,ω-alkylenediamine, a poly(thiol) moiety, a mono- or poly-alkylene-X moiety, or when R═C is a strained ring having at least 1× moiety as part of the ring; 
 X is N, S or O; 
 N c  is the multiplicity of the core and is from 1 to 1,000; 
 y is the number of macrocyclic loops and is from 1 to Z/2; 
 q is from 1-3; 
 Z is the surface of the dendrimer or dendron and is a poly(ester)- or poly(ether)-substituted terminal functionality, which may be from 1 to the theoretical number possible. 
 
       
     
     
         2 . The dendrimers or dendrons of  claim 1  wherein Z is poly(ester)- or poly(ether)-(acrylate, amine, piperazine, epoxy, aziridine, thioether or morpholine) moiety or any functionality derived from nucleophilic addition or reaction with an epoxy, acrylate, thioether, or aziridine moiety. 
     
     
         3 . The dendrimers or dendrons of  claim 1  wherein y is 1 or 2. 
     
     
         4 . The dendrimers or dendrons of  claim 1  wherein X is N. 
     
     
         5 . The dendrimers or dendrons of  claim 1  wherein the core is a mono-alkyl amine, an α,ω-alkylenediamine, a polyalkylene amine, a poly(thiol), or a poly(epoxy) core. 
     
     
         6 . A process for making the dendrimers and dendrons of  claim 1  wherein the compounds of Formula I are prepared by reacting a dendrimer or dendron core having one or more core-XR functionalities as defined in  claim 1  available for reaction with a branch cell reagent, where the molar ratio of branch cell reagent to core-XR is from about 0.5:1 to about 2:1, in the presence of a suitable solvent. 
     
     
         7 . The process of  claim 6  wherein the core is EDA, HDA, DETA, TREN, PETGE, TMPTGE, PEHAM, PAMAM or PEI. 
     
     
         8 . The process of  claim 1  or  7  wherein the surface group terminal functionality is a poly(ester)- or poly(ether)-(acrylate, amine, piperazine, epoxy, aziridine, thioether, or morpholine) moiety. 
     
     
         9 . The process of  claim 6  wherein the branch cell reagent is PTA, PETGE, TMPTA, TMPTGE, PPT, TREN or DETA. 
     
     
         10 . The process of  claim 6  wherein the solvent is methanol. 
     
     
         11 . The process of  claim 6  wherein the core is a mono-alkyl amine core and the branch cell reagent is PTA, PETGE, TMPTA, PPT or TMPTGE and the molar ratio of branch cell reagent to core-XR functionality is from about 0.5:1 to about 1:1. 
     
     
         12 . The process of  claim 6  wherein the core is an α,ω-alkylenediamine core, the branch cell reagent is PTA, PETGE, TMPTA, PPT or TMPTGE and the molar ratio of branch cell reagent to core-XR functionality is about 2:1. 
     
     
         13 . A method of using dendrimers or dendrons as claimed in any one of  claims 1 - 5  as sensors or detection research reagents or f as in vivo, in vitro or ex vivo diagnostic materials. 
     
     
         14 . A method of using dendrimers or dendrons as claimed in any one of  claims 1 - 5  as transfection agents in research or as therapeutic or diagnostic agents. 
     
     
         15 . A method of using dendrimers or dendrons as claimed in any one of  claims 1 - 5  as additives in cosmetic, ink, toner, plastic, paper, or coating applications. 
     
     
         16 . A method of using dendrimers or dendrons as claimed in any one of  claims 1 - 5  as a filtration material in water remediation applications. 
     
     
         17 . A method of using dendrimers or dendrons as claimed in any one of  claims 1 - 5  as agents in therapeutic applications. 
     
     
         18 . A method of using dendrimers or dendrons as claimed in any one of  claims 1 - 5  as chelating agents. 
     
     
         19 . The dendrimers or dendrons of  claim 18  where the chelate or complex is formed at any location Core, X, or Z on the dendrimer or dendron with: (a) metals or their ions, (b) nucleic acids, (c) dyes or pigments, (d) pharmaceuticals, (e) cosmetic ingredients or (f) combinations of these chelates with the dendrimer or dendron.